WO2017150340A1 - Particules composites, poudre composite, procédé de fabrication de particules composites et procédé de fabrication d'élément composite - Google Patents

Particules composites, poudre composite, procédé de fabrication de particules composites et procédé de fabrication d'élément composite Download PDF

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WO2017150340A1
WO2017150340A1 PCT/JP2017/006879 JP2017006879W WO2017150340A1 WO 2017150340 A1 WO2017150340 A1 WO 2017150340A1 JP 2017006879 W JP2017006879 W JP 2017006879W WO 2017150340 A1 WO2017150340 A1 WO 2017150340A1
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composite
powder
phase
ceramic
particle
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PCT/JP2017/006879
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English (en)
Japanese (ja)
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秀峰 小関
古谷　匡
大樹 進野
謙一 井上
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日立金属株式会社
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Priority to JP2018503089A priority Critical patent/JP6780697B2/ja
Priority to EP17759806.7A priority patent/EP3425072A4/fr
Priority to US16/080,730 priority patent/US10858295B2/en
Publication of WO2017150340A1 publication Critical patent/WO2017150340A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/148—Agglomerating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/18—Non-metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/34—Process control of powder characteristics, e.g. density, oxidation or flowability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/141—Processes of additive manufacturing using only solid materials
    • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62802—Powder coating materials
    • C04B35/62842—Metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/25—Direct deposition of metal particles, e.g. direct metal deposition [DMD] or laser engineered net shaping [LENS]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3839—Refractory metal carbides
    • C04B2235/3847—Tungsten carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
    • C04B35/5626—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on tungsten carbides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the present invention relates to composite particles, composite powders, and composite particle manufacturing methods, and in particular, composite particles, composite powders, composite particle manufacturing methods, and composite members having high strength and suitable for three-dimensional additive manufacturing. It relates to a manufacturing method.
  • Composite powders of ceramic particles and metal particles typified by cemented carbide and the like are used for various applications such as sintered body forming members and sprayed members.
  • Cited Document 1 at least a part of the composite particles, which can be applied to the forming material of the sintered body and the abrasive grains in addition to the thermal spraying, has a maximum value of 10 mN or more at a load speed of 15.0 mN / s.
  • grains characterized by not showing a breaking point in the stress-strain diagram obtained when the compressive load which increases to this extent are given are disclosed.
  • Cited Document 2 in order to improve mechanical strength, in order to uniformly distribute Co in the cemented carbide powder, the number of Co powders of 100 nm or more is reduced to a ratio of 4% or less of the total number of Co powders.
  • a controlled cemented carbide powder is disclosed.
  • composite particles composed of ceramic particles and metal particles are excellent in high-temperature strength, they are also suitable as materials for hot and cold molds.
  • As the mold manufacturing process a sintering process widely used in cemented carbide for cutting tools is known. However, thermal deformation is likely to occur during sintering, and the number of man-hours required for subsequent die cutting Is considered to be unsuitable because of its enormous volume.
  • a layered manufacturing method that can form a structure into an arbitrary shape without causing a large deformation in a mold by locally melting and solidifying a powder of metal or the like with a laser or the like has attracted attention.
  • the composite particles used for additive manufacturing are required to have high strength so as to prevent clogging of the supply nozzle due to deformation of the particles and prevent the powder from being destroyed during additive manufacturing.
  • An object of the present invention is to provide a high-strength composite particle, a composite powder, a method for manufacturing the composite particle, and a method for manufacturing a composite member using the composite powder, which are suitable for additive manufacturing and the like.
  • One aspect of the present invention is a composite particle comprising a ceramic phase and a metal phase
  • the composite particle is a composite particle having a cross-section with a porosity of 45% or less in an area ratio and a metal phase area ratio of 20% or more when the total area of the ceramic phase and the metal phase is 100%.
  • the area ratio of the ceramic phase when the total area of the ceramic phase and the metal phase in the range of 0.03d (d is an approximate circular diameter of the composite particle) from the surface is 100%,
  • the area ratio of the ceramic phase is preferably larger than the area ratio of the ceramic phase when the total area of the ceramic phase and the metal phase in the entire cross section of the composite particle is 100%.
  • Another aspect of the present invention is a composite powder including a plurality of the composite particles.
  • D50 in the volume cumulative particle size distribution of the composite powder is preferably 30 to 150 ⁇ m.
  • Another embodiment of the present invention is a method for producing composite particles including a ceramic phase and a metal phase, A step of wet mixing ceramic powder and metal powder in a volume ratio of 7: 3 to 2: 8 to obtain a mixed powder; A step of dry granulating the mixed powder to obtain granulated particles; A step of heat-treating the granulated particles at a temperature T within the range of the following (1) to obtain composite particles.
  • Ts solidus temperature of metal particles
  • the average particle size of the ceramic powder is preferably 0.1 to 20 ⁇ m.
  • a composite member is obtained by an additive manufacturing method in which the composite powder is melted and solidified.
  • the composite particle composed of two phases of the ceramic phase and the metal phase according to the present invention is a composite particle in which two phases of a hard ceramic phase as a structure and a metal phase as a binder (binding phase) are mixed.
  • the composite particles are characterized by combining the advantages of the ceramic phase (excellent strength) and the advantages of the metal phase (high ductility and toughness).
  • the ceramic phase of the composite particles of the present invention includes W (tungsten), Cr (chromium), Mo (molybdenum), V (vanadium), Zr (zirconium), Al (aluminum), Si (silicon), and Nb (niobium).
  • Ta (tantalum) and Ti (titanium) are preferably selected from at least one carbide, nitride, carbonitride, oxide and boride.
  • the metal phase of the composite particles of the present invention is preferably selected from at least one of Co (cobalt), Ni (nickel), Fe (iron), W (tungsten), and Mo (molybdenum).
  • WC—Co composite particles in which tungsten carbide (WC) is selected for the ceramic phase and Co is selected for the metal phase are selected.
  • FIG. 1 shows an appearance photograph of the composite particles of the present invention
  • FIG. 2 shows a cross-sectional photograph of the composite particles of the present invention.
  • One of the characteristics of the composite particles of the present invention is that the area ratio of the metal phase is 20% or more when the total area of the ceramic phase and the metal phase is 100% in the cross section of the particle.
  • the toughness of the composite particles can be further increased.
  • the area ratio of the metal phase is preferably 25% or more, the area ratio of the metal phase is more preferably 30% or more, and the area ratio of the metal phase is more preferably 40% or more.
  • the area ratio of the metal phase is preferably 80% or less, and more preferably 65% or less.
  • the area ratio of the metal phase is less than 20%, the characteristics of the ceramic phase become strong, and the particles tend to be destroyed at the time of the layered modeling, and the toughness of the modeled body produced by the layered modeling becomes small.
  • the area ratio of the metal phase is more than 80%, the characteristics of the metal phase become strong, and the particles tend to be deformed at the time of layered modeling, and the strength of the modeled body produced by the layered modeling becomes small.
  • the cross section of the particle is a cross section passing through the vicinity of the center of the particle (substantially central cross section). The center means the geometric center or centroid of the particle.
  • FIG. 2 is a cross-sectional view of the composite particle of the present invention taken by the above measurement method.
  • the outer diameter of the one composite particle is measured (for example, measured with a scanning electron microscope (SEM) photograph as shown in FIG. 1), and ⁇ 10% of the outer diameter is measured.
  • SEM scanning electron microscope
  • the composite particles of the present invention are further characterized in that the porosity in the cross section of the particles is 45% or less in terms of area ratio.
  • the porosity is preferably 40% or less, and more preferably 35% or less.
  • the porosity is an area ratio occupied by the pores 4 when the cross-sectional area of the composite particles is set to 100% in FIG. 2, and the cross-sectional area of the composite particles is represented by a dotted line in FIG.
  • the term “projection” is defined as a ratio G / H value of 1.5 or more between the height G of the projection and the root width H of the projection.
  • the area ratio of the ceramic phase in the range of 0.03d from the surface toward the center of the particle when the total area of the ceramic phase and the metal phase is 100% in the cross section of the particle It is preferable that it is larger than the area ratio of the ceramic phase in the whole cross-section of the composite particles.
  • d is the diameter of the approximate circle C (a perfect circle that includes the particle inside and has the smallest diameter) in the cross-sectional view of the composite particle.
  • the area ratio of the ceramic phase in the range of 0.05d is larger than the area ratio of the ceramic phase in the entire cross-section of the composite particles.
  • a layer in which the area ratio of the ceramic phase in the range of 0.03d (or 0.05d) from the surface toward the center of the particle is larger than the area ratio of the ceramic phase in the entire cross section of the composite particle (hereinafter referred to as ceramic).
  • the concentration ratio of the ceramic phase is more preferably 60% or more, and even more preferably 70% or more.
  • the area ratio of the ceramic phase in the ceramic concentrated layer is preferably 95% or less, more preferably 92% or less. Due to the above characteristics, the strength in the vicinity of the surface of the composite particles can be further increased. Thereby, when producing a layered object using the composite particles of the present invention, it becomes difficult to deform during layered object modeling, and the fluidity in the injection nozzle can be improved.
  • the ceramic phase area ratio is 60% or more, and the formation range of the ceramic concentration layer is 0.03d or more. Particularly preferred.
  • FIGS. 2 and 3 an example of the measuring method of the ceramic concentrated layer in the range of 0.03d from the surface toward the center is shown below. As shown in FIGS. 2 and 3, a sector F having a circular arc length of 5% of the approximate circumference is drawn with the approximate circle center Oc as a center point, and the intersection of the two sides of the sector F and the composite particle surface 10 is defined as an intersection.
  • the virtual boundary line K is similar to the particle outline 10a drawn at a position 0.03d away from the outline 10a of the particle between P and Q in the direction of the approximate circle center Oc. Represents a line.
  • the virtual boundary line K may be obtained by translating the outline 10a. This parallel movement may be performed by moving the substantially midpoint of the outline 10a by 0.03d in the direction of the approximate circle center Oc.
  • a position 0.05d away from the outline 10a of the particle between P and Q toward the approximate circle center Oc The virtual line similar to the outer shape 10a of the particle drawn in (1) may be set as the virtual boundary line K. Then, the proportion of the ceramic phase when the area of the composite alloy phase including the ceramic phase 2 and the metal phase 3 excluding the voids 4 in the region surrounded by PQRS is set to 100% is measured. The above measurement is performed at four locations so that the ranges do not overlap with the same composite particle, and the average area ratio of the ceramic phase at that time is defined as the area ratio of the ceramic phase in the range of 0.03d.
  • the area ratio of the ceramic phase in the range of 0.03d from the surface toward the center of the particle is the ratio of the area ratio of the ceramic phase in the range of 0.1d from the surface to the center of the particle.
  • the value is preferably 1.2 times or more. More preferably, it is 1.3 times or more, and still more preferably 1.4 times or more.
  • the area ratio of the ceramic phase in the range of 0.05d from the surface toward the center of the particle is 1.15 times or more than the area ratio of the ceramic phase in the range of 0.1d from the surface toward the center of the particle. It is preferable to be a value of. More preferably, it is 1.25 times or more, and further preferably 1.35 times or more.
  • the composite particles of the present invention preferably have a compressive strength of, for example, 20 MPa or more.
  • a more preferable compressive strength is 50 MPa or more.
  • the ceramic particles constituting the ceramic phase in the cross section of the composite particle of the present invention preferably have a polygonal shape with a circularity of 0.6 or more. A more preferable circularity is 0.7 or more. Due to the above characteristics, the strength of the composite particles of the present invention can be further improved.
  • the composite powder of the present invention is a composite powder comprising a plurality of the composite particles of the present invention described above. Specifically, if the composite particles of the present invention contain 40 vol% or more of the composite particles of the present invention, an advantageous effect can be achieved, for example, at the time of additive manufacturing.
  • the powder added to the composite powder of the present invention other than the composite particles of the present invention include metal powder and carbon powder having a particle diameter equivalent to that of the composite powder.
  • the composite powder of the present invention preferably has a D50 diameter d of 30 to 150 ⁇ m in the volume cumulative particle size distribution.
  • d is less than 30 ⁇ m, for example, the efficiency of the layered modeling decreases because the layered modeling speed decreases.
  • d is larger than 150 ⁇ m, for example, the surface accuracy of the layered object tends to decrease.
  • the present invention is a method for producing composite particles comprising a ceramic phase and a metal phase, A step of wet mixing ceramic powder and metal powder in a volume ratio of 7: 3 to 2: 8 to obtain a mixed powder; A step of dry granulating the mixed powder to obtain granular granulated particles; A step of heat-treating the granulated particles at a temperature T within the range of the following (1) to obtain composite particles.
  • Ts solidus temperature of metal powder
  • a ceramic powder and a metal powder are wet-mixed together with a liquid such as ethanol or water using a mixer such as an attritor or a ball mill to obtain a slurry-like mixed powder.
  • a mixer such as an attritor or a ball mill to obtain a slurry-like mixed powder.
  • the volume ratio of the ceramic powder to the metal powder is adjusted within a range of 7: 3 to 2: 8. When it deviates from the above-mentioned range, it is difficult to obtain a high-strength powder.
  • a wax such as paraffin of less than 5 parts by mass is added to 100 parts by mass in total of the ceramic powder and the metal powder.
  • the amount of the wax to be added is 5 parts by mass or more, voids generated in the composite particles after the heat treatment described later increase, and the particle strength may decrease.
  • the addition amount of the wax is too small, it is difficult to obtain a granular composite powder at the time of dry granulation described later. Therefore, the addition amount of the wax is 0.1 parts by mass with respect to the total mass ratio of the ceramic powder and the metal powder. The above is preferable.
  • the average particle size of the ceramic powder used in the production method of the present invention is preferably 0.1 to 20 ⁇ m, and more preferably 0.1 to 10 ⁇ m.
  • the average particle size of the metal powder is preferably 0.1 to 5 ⁇ m, for example.
  • the average particle diameter of the powder can be measured, for example, by a laser diffraction method. In the present embodiment, the particle diameter (Fischer diameter) measured using a Fischer sub-sieve sizer described in JIS-H-2116 (2002) was used as the average particle diameter.
  • a spray dryer or the like can be applied.
  • a spray dryer it is possible to obtain granulated particles that are more uniform and nearly spherical.
  • After drying and granulating with a spray dryer it is preferable to classify using a sieve or airflow classification.
  • the solidus temperature of the metal powder is the melting point of the metal when the selected metal powder is one type, and the solidus temperature of the alloy in which they are mixed when two or more types are selected.
  • Ts Co solidus temperature
  • the upper limit of the preferable heat treatment temperature is 1350 ° C.
  • TiCN—Ni composite particles Ni solid phase temperature (Ts): about 1455 ° C.
  • the lower limit of the preferable heat treatment temperature is 1047 ° C. It is. This is because sinterability between TiCNs is low and the sintering of the TiCNs itself is difficult to proceed, so that heat treatment can be performed at a temperature higher than that of the WC-Co composite particles.
  • the atmosphere at the time of the heat treatment of the present invention is not particularly limited, for example, it is preferably carried out under a reduced pressure of a non-oxidizing atmosphere such as argon or nitrogen.
  • a composite member having good surface accuracy with few cracks can be obtained by using a layered molding method in which powder deposition, melting and solidification are repeated.
  • An existing apparatus can be used as the additive manufacturing apparatus at this time.
  • a laser is selected as a heat source for melting powder, but it is not always necessary to use a laser, and the same additive manufacturing can be suitably performed using an electron beam, arc, or plasma.
  • the powder of the present invention can be applied to a powder bed method in which the powder is spread in advance and heated by irradiation, or a direct metal deposition method in which the powder is directly sprayed on a heat source and welded to a substrate.
  • Example 1 First, tungsten carbide powder (average particle diameter 0.8 ⁇ m) and cobalt powder (average particle diameter 0.6 ⁇ m) were used as raw material powders, and tungsten carbide powder and cobalt powder were weighed so as to have a volume ratio of 6: 4. . Then, a small amount of carbon powder and paraffin wax were added to the weighed powder, and the mixture was put together with ethanol into an attritor and wet-mixed to obtain a mixed powder slurry. And the slurry of the obtained mixed powder was dried and granulated with the spray dryer, and the granulated powder was obtained. No. which is an example of the present invention. Sample 1 was degreased and then heat treated at 1260 ° C.
  • the average particle diameter of raw material powder is an average particle diameter measured with the Fischer sub sieve sizer.
  • a laser diffraction / scattering particle size distribution measuring device “Microtrack MT3000II” manufactured by Microtrack Bell was used.
  • the cross-section of the composite particles is obtained by vacuum impregnation into a two-component room temperature curing type epoxy resin, solidified, and ion milled with a JEOL cross-section polisher together with the resin, and then a diameter corresponding to D50 in the volume cumulative particle size distribution.
  • the cross section of the composite particles having a diameter falling within a range of ⁇ 10% was observed with a JEOL field emission scanning electron microscope. No. obtained 1 is shown in FIG.
  • a cross-sectional photograph of 11 is shown in FIG.
  • the area ratio of the ceramic phase, the area ratio of the metal phase, and the porosity were determined using image analysis software “Scandium Ver. 5.2” manufactured by Seika Sangyo Co., Ltd.
  • the compressive strength of the produced particles was measured using a micro compression tester “MCT-510” manufactured by Shimadzu Corporation. The measurement results are shown in Table 1.
  • No. 1 composite particle has an area ratio of the ceramic phase of 47% in the entire cross-sectional area, and has a ceramic concentrated layer in the range of 0.03d from the particle surface.
  • the area ratio of the ceramic phase in the ceramic concentrated layer is 72 Similarly, the area ratio of the ceramic phase in the ceramic concentrated layer in the range of 0.05d from the particle surface was 70%, and the area ratio of the ceramic phase in the range of 0.1d from the particle surface was 51%. It was. No. In the composite particle of No. 11, the area ratio of the ceramic phase in the entire cross-section is 36%, the area ratio of the ceramic phase in the range of 0.03d from the particle surface is 53%, and the ceramic phase in the range of 0.05d from the particle surface. The area ratio was 51%, and the area ratio of the ceramic phase in the ceramic phase in the range of 0.1 d from the particle surface was 45%.
  • No. with low porosity Sample No. 1 has a high porosity. 11, no. Compared with 12 samples, it showed high compressive strength, and it was confirmed that it was a high-strength powder. Subsequently, the manufactured No. 3 was used. 1, no. 12, no. 13 composite powders were put into a laser clad additive manufacturing apparatus, and a 45 mm x 15 mm x 8 mm height model was produced under the conditions of a laser output of 1200 W, a modeling speed of 1.7 mm / min, and a powder supply rate of 2 g / min. The appearance was observed. As a result, no. The molded article using the composite powder No.
  • Example 2 As raw material powders, titanium carbonitride powder (average particle size 1.2 ⁇ m) and nickel powder (average particle size 2.5 ⁇ m) are used, and the titanium carbonitride powder and nickel powder are weighed so that the volume ratio is 5: 5. did. Then, a small amount of carbon powder and paraffin wax were added to the weighed powder, and the mixture was put together with ethanol into an attritor and wet-mixed to obtain a mixed powder slurry. And the slurry of the obtained mixed powder was dried and granulated with a spray dryer to produce a granulated powder, and the obtained granulated powder was heat treated at 1300 ° C. after degreasing. A plurality of composite particles 2 was obtained.
  • the titanium carbonitride powder and the nickel powder were weighed so that the volume ratio was 9: 1.
  • the granulated powder was prepared using the same process as in No. 2, the granulated powder was degreased and heat treated at 1450 ° C. A plurality of composite particles of 14 were obtained.
  • the average particle diameter of the raw material powder is an average particle diameter measured with a Fischer sub-sieve sizer. No. obtained 2, No.
  • the volume cumulative particle size distribution D50 and the compressive strength were measured using the same measuring apparatus as in Example 1. The results are shown in Table 2.
  • No. The porosity of the sample of No. 2 is 45% or less in area ratio, and the area ratio of the metal phase is 20% or more.
  • the porosity of the composite powder No. 14 was 45% or less in terms of area ratio, and the area ratio of the metal phase was less than 20%.

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Abstract

La présente invention se rapporte à des alliages à haute résistance/ductilité élevée et, en particulier, à des particules composites à haute résistance comprenant une phase céramique et une phase métallique, à une poudre composite, à un procédé de fabrication de particules composites et à un procédé de fabrication d'un élément composite. Les particules composites comprennent une phase céramique et une phase métallique, les particules composites étant caractérisées en ce que la porosité est inférieure ou égale à 45 % en termes de taux surfacique en coupe transversale et en ce que la proportion surfacique de la phase métallique, où la surface totale de la phase céramique et de la phase métallique est de 100 %, est d'au moins 20 %. La poudre composite est caractérisée en ce qu'elle comprend une pluralité des particules composites.
PCT/JP2017/006879 2016-03-01 2017-02-23 Particules composites, poudre composite, procédé de fabrication de particules composites et procédé de fabrication d'élément composite WO2017150340A1 (fr)

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JP2018503089A JP6780697B2 (ja) 2016-03-01 2017-02-23 複合粒子、複合粉末、複合粒子の製造方法、および複合部材の製造方法
EP17759806.7A EP3425072A4 (fr) 2016-03-01 2017-02-23 Particules composites, poudre composite, procédé de fabrication de particules composites et procédé de fabrication d'élément composite
US16/080,730 US10858295B2 (en) 2016-03-01 2017-02-23 Composite particles, composite powder, method for manufacturing composite particles, and method for manufacturing composite member

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JP2018090841A (ja) * 2016-11-30 2018-06-14 セイコーエプソン株式会社 エネルギー線焼結用粉末、エネルギー線焼結用粉末の製造方法および焼結体の製造方法
JP2020019203A (ja) * 2018-07-31 2020-02-06 パナソニック株式会社 セラミックス焼結体の製造方法
EP3479932B1 (fr) * 2017-11-03 2021-12-01 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung Procédé de fabrication de granules frittées à base de métal dur

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JP2018090841A (ja) * 2016-11-30 2018-06-14 セイコーエプソン株式会社 エネルギー線焼結用粉末、エネルギー線焼結用粉末の製造方法および焼結体の製造方法
EP3479932B1 (fr) * 2017-11-03 2021-12-01 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung Procédé de fabrication de granules frittées à base de métal dur
JP2020019203A (ja) * 2018-07-31 2020-02-06 パナソニック株式会社 セラミックス焼結体の製造方法

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EP3425072A1 (fr) 2019-01-09
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EP3425072A4 (fr) 2019-09-25
JP6780697B2 (ja) 2020-11-04
US20190016641A1 (en) 2019-01-17

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